First Published in August 1998
National Pollutant Inventory
Emission Estimation
Technique Manual
for
Pulp and Paper
Manufacturing
Approved 25/6/98
1
EMISSION ESTIMATION TECHNIQUES
FOR
PULP AND PAPER MANUFACTURING
TABLE OF CONTENTS
1.0 INTRODUCTION 3
2.0 PROCESS DESCRIPTION 4
3.0 EMISSION ESTIMATION 4
3.1 Emissions To Air 5
3.2 Emissions To Water 5
3.3 Emissions To Land 6
3.4 Process Inputs And Emission Outputs 6
4.0 EMISSION FACTOR RATING 10
5.0 EMISSION FACTORS 11
5.1 Using Sampling Data 11
5.2 Using Emission Factors 13
5.3 Using Fuel Analysis Data 20
5.4 Using CEMS Data 21
5.5 Using Predictive Emissions Monitoring 23
6.0 CONTROL TECHNOLOGIES 23
6.1 Kraft Pulping 24
6.2 Acid Sulphite Pulping 24
7.0 REFERENCES 26

3
1.0 Introduction
The purpose of all Emission Estimation Technique (EET) Manuals in this
series is to assist Australian manufacturing, industrial and service facilities
to report emissions of listed substances to the National Pollutant
Inventory (NPI). This Manual describes the procedures and recommended
approaches for estimating emissions from facilities engaged in pulp and
paper product manufacturing.
The pulp and paper product manufacturing activities covered in this
Manual apply to facilities primarily engaged in the manufacture of paper
pulp, and the conversion of this pulp into paper, cardboard, newsprint,
paperboard, and solid fibreboard sheets.
EET MANUAL: Pulp and paper manufacturing
HANDBOOK: Paper and paper product manufacturing
- Pulp, paper and paperboard manufacturing
- Solid paperboard container manufacturing
- Corrugated paperboard container manufacturing
- Paper bag and sack manufacturing
- Paper product manufacturing n.e.c.
ANZSIC CODES: 233 (including 2331, 2332, 2333, 2334, and 2339)
This Manual was drafted by the NPI Unit of the Queensland Department
of Environment on behalf of the Commonwealth Government. It has
been developed through a process of national consultation involving State
and Territory environmental authorities and key industry stakeholders.
Approved 25/6/98
4
2.0 Process Description
The pulp and paper product manufacturing activities covered by this EET
Manual include the production of commodity grades of paper pulp,
printing and writing papers, sanitary tissue, industrial-type papers,

5
You are able to use emission estimation techniques that are not outlined
in this document. You must, however, seek the consent of your relevant
environmental authority. For example, if you already undertake direct
measurement, you may use this information for NPI reporting purposes
(if you do not undertake direct measurement, the NPI does not require you
to do so).
3.1 Emissions To Air
Air emissions may be categorised as :
Fugitive emissions
These are emissions that are not released through a vent or stack.
Examples of fugitive emissions include dust from stockpiles, volatilisation
of vapour from vats or open vessels, and material handling. Emissions
emanating from ridgeline roof-vents, louvres, and open doors of a
building as well as equipment leaks, and leaks from valves and flanges are
also examples of fugitive emissions. Emission factor EETs are the usual
method for determining losses through fugitive emissions.
Point source emissions
These emissions are exhausted into a vent or stack and emitted through a
single point source into the atmosphere. An air emissions control device
such as a carbon adsorption unit, scrubber, baghouse, or afterburner may be
used prior to the atmospheric release. Table 1 highlights common air
emissions from pulp and paper processes.
Table 1. Common Air Emissions from Pulp and Paper Processes
Source Effluent Characteristics
Kraft recovery furnace Particulate matter (PM
10
)
Fly ash from wood waste and coal fired
boilers

Solids, BOD, colour
Chip digester and liquor evaporator
condensate
Concentrated BOD, reduced sulphur
compounds
‘White waters’ from pulp screening,
thickening, and cleaning
Large volumes of water with suspended
solids, can have significant BOD
Bleach plant washer filtrates BOD, colour, chlorinated organic
compounds
Paper machinewater flows Solids, often precipitated for reuse
Fibre and liquor spills Solids, BOD, colour
USEPA 1995, Pulp and Paper Industry Sector Notebook Project
3.3 Emissions To Land
Emissions of substances to land on-site include solid wastes, slurries,
sediments, spills and leaks, storage and distribution of liquids, and the use
of chemicals to control various elements of the environment where these
emissions contain listed substances. These emission sources can be broadly
categorised as :
• surface impoundments of liquids and slurries
• unintentional leaks and spills.
3.4 Process Inputs And Emission Outputs
Kraft chemical pulping and traditional chlorine-based bleaching are both
commonly used, and may generate significant emissions. Emissions from
mechanical, semi-chemical, and secondary fibre pulping are small when
compared to kraft chemical pulping, which is the most significant source
of air pollutant emissions. Pollutant emissions from chlorine bleaching,
and chlorinated by-products (ie. chloroform and dioxin), are particular
problems due to their persistence, non-biodegradability, and toxicity.

Bleaching Y
Non-condensable Gases:
Collected, not Incinerated X
2
X
Incinerated X
2
Y
Turpentine Production Y
Tall Oil Recovery Y
Chemical Recovery
Evaporation Y Y
Black Liquor Oxidation X
Recovery Furnace X X X X Y
Recausticising X Y Y Y
Lime Kiln X Y X X Y
Pulp Drying Y
Boilers (fuel dependent) Y X X X
Wastewater Treatment X
USEPA 1995, Pulp and Paper Industry Sector Notebook Project
Major sources are marked with an X, minor sources are marked with anY.
1
Depends if the gases are collected.
2
Depends if the emissions are treated in a scrubber or if incineration takes place in the kiln.
Approved 25/6/98
8
Table 4. Kraft Chemical Pulped-Chlorine Bleached Paper Production
Process
Step

chlorinated organic
compounds (dioxins
and furans), VOCs
(terpenes, alcohols,
phenols, methanol,
acetone, chloroform,
methyl ethyl ketone)
Water
chlorinated organic
compounds (dioxins
and furans), VOCs
(terpenes, alcohols,
phenols, methanol,
acetone, chloroform,
methyl ethyl ketone)
Air
Cooking
chemicals:
Na
2
S, NaOH,
white liquor
reduced sulphur
compounds, organo-
chlorine compounds
Bleaching Chemical
pulp
Bleached
pulp
chlorinated organic

pulp
Paper /
paperboard
product
organic compounds Water
acetone
Wastewater
Treatment
Process
wastewaters
Treated
effluent
sludges containing
listed substances
Solid
Approved 25/6/98
9
Table 4. Kraft Chemical Pulped-Chlorine Bleached Paper Production
(cont’d)
Process
Step
Material
Inputs
Process
Outputs
NPI Listed Substance
Emissions
a
Emission
Media

Furnace
Strong black
liquor
Smelt PM
10
, TRS, SO
2
Air
Energy
Calcining Lime mud Lime PM
10
Air
Adapted from USEPA 1995, Pulp and Paper Industry Sector Notebook Project
a
Emissions may differ significantly based on mill processes and material inputs.
b
Chlorate only significantly produced in mills with high rates of chlorine dioxide
substitution.
Pulp and paper manufacturing processes in Australia vary significantly,
and each reporting facility will handle a different range of substances on
the NPI reporting list as a result of the differing processes used. As each
facility in Australia is unique, you are encouraged to develop process flow
diagrams for your own operations detailing the input of materials and
listed substances, and the waste sources and emissions resulting from the
operation of each process. The flow diagrams and tables contained in this
section are merely a guide to some of the possible emissions that may arise
from different processes under different conditions.
Approved 25/6/98
10
4.0 Emission Factor Rating

E - Poor
U - Unrated
Estimating your facility’s emissions based on emission factors only, and
without taking into account any control measures, may have an
uncertainty as high as 100%.
Other EETs, such as release calculations based on mass balance of solvent
consumption and without taking into account control measures, may
have an uncertainty of 50%.
An EET based on an audit or direct measurement, and taking into account
control measures, may have an uncertainty of 20% .
Approved 25/6/98
11
5.0 Emission Factors
5.1 Using Sampling Data
Stack sampling test reports often provide emissions data in terms of kg/hr
or grams /dscm (dry standard cubic metre). Annual emissions for NPI
reporting can be calculated from this data using Equations (1) or (2)
overleaf. Stack tests for NPI reporting should be performed under
representative (ie.normal) operating conditions. As stated previously, you
may wish to undertake direct measurement in order to report to the NPI,
particularly if you already do so in order to meet other regulatory
requirements. However, the NPI does not require you to undertake
additional sampling and measurement.
You should be aware that some tests required for State and Territory
license conditions may need to be undertaken when operating under
maximum emissions rating. Consequently, emissions are likely to be
higher than when operating under normal conditions.
This Section shows how to calculate emissions in kg/hr based on stack
sampling data, and how to convert this to an annual emissions figure.
Calculations involved in determining PM

Fuel use Q
f
typically, kg/hr
PM
10
concentration C
PM
grams/dscm
Metered volume at standard
temperature and pressure
V
m, STP
dscm
Moisture R percent
Temperature T degrees Celsius
Paper pulp production A tonnes/year
Annual operating hours OpHrs hours/year
QLD Department of Environment 1998
Approved 25/6/98
12
An example summary of a test method is shown in Table 6. The table
shows the results of three different sampling runs conducted during one
test event. The source parameters measured as part of the test run include
gas velocity and moisture content, which are used to determine exhaust
gas flow rates in dscms.
The filter weight gain is determined gravimetrically and divided by the
volume of gas sampled (as shown in Equation 1) to determine the PM
concentration in grams per dscm. Please note that this example does not
present the condensable PM emissions.
Pollutant concentration is then multiplied by the volumetric flow rate to

Q
d
= stack gas volumetric flow rate (dscms)
3 600 = seconds per hour
1 000 = grams per kg
Table 6. Stack Sample Test Results
Parameter Symbol Test 1 Test 2 Test 3
Total sampling time (secs) sec 7 200 7 200 7 200
Moisture collected (grams) grams 395.6 372.6 341.4
Filter catch (grams) C
f
0.0851 0.0449 0.0625
Average sampling rate
(dscms)
dscms 1.67 x 10
-4
1.67 x 10
-4
1.67 x 10
-4
Standard metered volume
(dscm)
V
m, STP
1.185 1.160 1.163
Volumetric flow rate
(acms or dscms)
Q
a
or Q

= 0.072 grams/dscm
E
PM
=C
PM
x Q
d
x 3 600 ÷ 1 000
= 0.072 x 8.48 x (3 600seconds/hr) ÷ (1kg/1 000grams)
= 2.20 kg/hour
The information from some stack tests may be reported in kilograms of
particulate per kilograms of exhaust gas (wet). Use Equation (3) to calculate
the dry particulate emissions in kg/hr.
E
PM
= Q
a
÷ 1 000 x 3 600 x 1.2 (1 - R) x [293 ÷ (273 + T)] (3)
where:
E
PM
= hourly emissions in kg/hr of PM
Q
a
= actual cubic metres of exhaust gas per second (acms)
1 000 = 1 000 kg exhaust gas per kg of PM
3 600 = seconds per hour
1.2 = 1.2 kg/m
3
R = moisture content (%)

10
fraction can then be multiplied by the total PM emission rate
to produce a PM
10
number.
Emission factors developed from measurements for a specific mill or
process may sometimes be used to estimate emissions at other sites.
Should a company have several processes of similar operation and size,
and emissions were measured from one process source, an emission factor
could be developed and applied to similar sources. As previously
mentioned, it is advisable to have the emission factor reviewed and
approved by State or Territory environment agencies prior to its use for
NPI estimations.
Example 2.
Table 7 shows that 0.55kg of hydrogen sulphide at the multiple effect evaporator are
emitted for each tonne of air-dried pulp produced with no venting device in place. It
is assumed that the pulp mill operates for 1 500 hours per year.
EF
hydrogen sulphide
= 0.55kg/tonne
Pulp production rate = 100 tonnes/hour
H
2
S emissions = EF
hydrogen sulphide
x pulp production rate
= x operating time
= 0.55 x 100
= 55 kg/hr x (1 tonne ÷ 1 000kg)
x 1 500 hr/yr

(S
m
)
kg/t kg/t kg/t kg/t kg/t kg/t
Digester relief
and blow tank Untreated
b
ND ND 0.02 ND ND 0.6
Brown stock
washer Untreated
b
ND ND 0.01 ND ND 0.2
c
Multiple effect
evaporator Untreated
b
ND ND 0.55 ND ND 0.05
Recovery
boiler and
direct
evaporator
Untreated
d
3.5 5.5 6
e
ND ND 1.5
e
Venturi
scrubber
f

Mesh pad 0.1 ND 0.1
h
ND ND 0.15
h
Scrubber 4.02E-04
m
3.205E-03
m
0.1
h
1.045E-01
m
ND 0.15
h
ESP 1.495E-03
m
0.9505
m
ND 0.64
m
ND ND
Lime kiln
Untreated 0.15 0.05 0.25
j
ND 0.504E-04
m
0.1
j
Scrubber or
ESP ND 0.05 0.25

Usually reduced by 50% with black liquor oxidation and can be cut 95 - 99% when oxidation
is complete and recovery furnace is operated optimally.
f
Apply when venturi scrubber is used for direct contact evaporation, with no further
controls.
g
Use 7.5 kg/tonne when auxiliary scrubber follows venturi scrubber, and 1.5 kg/tonne when
it follows ESP.
h
Apply when recovery furnace is operated optimally to control total reduced sulphur (TRS)
compounds.
j
Usually reduced to 0.01kg/t ADP when water low in sulphides is used in smelt dissolving
tank and associated scrubber.
m
Usually reduced to 0.015kg/tonne ADP with efficient mud washing, optimal kiln
operation and added caustic in scrubbing water. With only efficient mud washing and
optimal process control, TRS compounds reduced to 0.04 kg/tonne ADP.
n
Includes knotter vents, brownstock seal tanks, etc. When black liquor oxidation is
included, emissions are 0.3 kg/t.
Table 8. Kraft Pulping Emission Factors for Particulate Matter (PM
10
)
Sources
Emission Factor (kg/t of Air-Dried Pulp)
Uncontrolled Controlled
Recovery boiler with a direct-contact
evaporator and an ESP
84 ND

kg/ADt 0.045 - evaporation kg/ADt 0.05
- foul condensates
used
kg/ADt 0.49 - black liquor oxidation kg/ADt 0.17
Bleaching kg/ADt 0.05 Recovery Furnace
Non-condensable
gases
- without direct contact
evaporator kg/ADt 0.14
- collected, not
incinerated
kg/ADt 0.5 - with direct contact
evaporator kg/ADt
0.53
- incinerated kg/ADt ND Recausticising kg/tonne
BLS
ND
Turpentine production kg/tonne
turpentine
0.05 - with clean condensates kg/tonne
BLS
0.031
Oxygen
delignification
reactors
kg/ADt 0.041
- with dirty condensates kg/tonne
BLS
0.88
USEPA. October 1996. Compilation of Air Pollutant Emission Factors, Volume 1:

carbon emission factors in Table 9. The processes of kraft pulping which are relevant to
Table 10 and where VOC emission factors are available are:
- washers/screens
- recovery furnace with direct contact evaporator
- recausticising
- turpentine production
- oxygen delignification reactors
- recovery furnace without contact evaporation
b
O-Xylene, M-Xylene, and P-Xylene emissions need to be added together and one value
reported for total xylene emissions.
Approved 25/6/98
19
Table 11. Emission Factors for Sulphite Pulping
a
Emission Factor
b
Source Base Control PM
10
SO
2
Factor
kg/ADUT kg/ADU
T
Rating
Digester /
blow pit or
dump tank
c
All

1 4.5 A
NH
3
Ammonia absorption and
mist eliminator
0.35 3.5 B
Na Sodium carbonate
scrubber
21C
Acid plant
f
NH
3
Scrubber Neg 0.2 C
Na Unknown
g
Neg 0.1 D
Ca Jensen scrubber Neg 4 C
Other
h
All None Neg 6 D
USEPA. October 1996. Compilation of Air Pollutant Emission Factors, Volume 1:
ADUT = air-dried unbleached tonne. Neg = negligible.
a
All factors represent long term average emissions.
b
Expressed as kg of substance emitted / air dried unbleached tonne of pulp produced.
c
Factors represent emissions after cook is completed and when digester contents are
discharged into blow pit. Some relief gases are vented from digester during cook cycle, but

Total VOCs 5 E-06 C
USEPA. October 1996. Compilation of Air Pollutant Emission Factors, Volume 1:
a
Units are kg of substance emitted / tonne of wood waste burned.
Approved 25/6/98
20
The Combustion in Boilers EET Manual is available for mills using this
form of combustion in pulp and paper production. This Manual covers
emissions from burning wood waste, coal, oil, and natural gas in a variety
of boilers and stokers and under different firing configurations. This, and
other Manuals should be available from your local environmental
authority.
5.3 Using Fuel Analysis Data
Fuel analysis can be used to predict SO
2
, metals, and other emissions based
on application of conservation laws, if fuel rate (Q
f
) is measured. The
presence of certain elements in fuels may be used to predict their presence
in emission streams. This includes elements such as sulphur which may
be converted into other compounds during the combustion process.
The basic equation used in fuel analysis emission calculations is the
following:
E
x
= Q
f
x pollutant concentration in fuel x ( MW
p

emissions can be calculated from oil combustion based
on fuel analysis results and the fuel flow information. The pulp mill is assumed to
operate 1500 hours per year.
E
SO2
= may be calculated using Equation (5)
Assume a given Q
f
= 2 000 kg/hr
Weight percent sulphur in fuel = 1.17
E
SO2
= Q
f
x pollutant concentration in fuel x (MW
p
÷ MW
f
)
= (2 000) x (1.17 ÷ 100) x (64 ÷ 32)
= 46.8kg/hr x tonne/1 000kg x 1 500 hr/yr
= 70.2 tonnes/year
Approved 25/6/98
21
5.4 Using CEMS Data
To monitor SO
2
, NO
x
, VOC, and CO emissions using a CEMS, you use a

for NPI emissions estimations.
Table 13. Example CEM Output Averaged for a Lime Kiln Firing Waste
Fuel Oil
Time O
2
Concentration (C)
(ppmvd)
Gas
Flow
Emission Rate (E)
(kg/hr)
Pulp
Rate (A)
(%V)
SO
2
NO
x
CO VOC
Rate
(Q) SO
2
NO
x
CO VOC
(tonnes
/ hour)
1 10.3 150.9 142.9 42.9 554.2 8.52 12.34 11.69 1.54 11.33 290
2 10.1 144.0 145.7 41.8 582.9 8.48 11.72 11.86 1.49 11.86 293
3 11.8 123.0 112.7 128.4 515.1 8.85 10.45 9.57 4.77 10.94 270

x OpHrs ÷ 1 000 (7)
where:
E
tpy,x
= annual emissions in tonnes/year of pollutant x
E
x
= hourly emissions in kg/hr of pollutant x
OpHrs= annual operating hours in hr/yr
Emissions in kilograms of pollutant per tonne of air-dried pulp produced
can be calculated by dividing the emission rate in kg/hr by the pulp
production rate (tonnes/hr) during the same period (Equation (8)) as
shown below. It should be noted that the emission factor calculated below
assumes that the selected time period (that is, hourly) is representative of
annual operating conditions, and longer time periods should be used for
NPI reporting where they are available. Use of the calculation is shown in
Example 4.
E
tpy,x
= E
x
÷ A (8)
where:
E
tpy,x
= emissions of pollutant x (kg/tonnes) per tonne of air-
dried pulp produced
E
x
= hourly emissions in kg/hr of pollutant x

E
tpy,SO2
= E
SO2
÷ A
= 13.22 ÷ 290
= 4.56 x 10
-2
kg SO
2
emitted per tonne of pulp produced
5.5 Using Predictive Emissions Monitoring
Emissions from the pulp and paper manufacturing process depend upon
several variables. For example, VOC process emissions for a given mill
may vary with several parameters including the type of fuel burned, the
relative quantities of various pulp constituents, the type of pulping
technique undertaken, the use of bleaching chemicals and processes, and,
the fuel combustion rate.
An example of predictive emissions monitoring that could be used to
develop a PEM protocol for acceptable NPI reporting would need to
account for the variability in these parameters, and consequently, may
require a complex testing algorithm.
To develop this algorithm, correlation testing of the process variables
could be conducted over a range of potential operating conditions for a
suite of listed NPI substances including VOCs and SO
2
. Based on the test
data, a mathematical correlation can be developed which predicts
emissions using the various parameters. This method may be cost
prohibitive for a single source and may need to be undertaken across the

the multiple-effect evaporator system is extended to replace the direct-
contact evaporator altogether. In both of these systems, sulphur emissions
from the recovery furnace/direct-contact evaporator can be reduced by
more than 99 percent.
Sulphur dioxide is emitted mainly from the oxidation of reduced sulphur
compounds in the recovery furnace. It is reported that the direct contact
evaporator absorbs about 75 percent of these emissions, and further
scrubbing can provide additional control.